JP4464356B2 - Heat-shrinkable milky film, shrink label and labeled container - Google Patents

Heat-shrinkable milky film, shrink label and labeled container Download PDF

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JP4464356B2
JP4464356B2 JP2005505780A JP2005505780A JP4464356B2 JP 4464356 B2 JP4464356 B2 JP 4464356B2 JP 2005505780 A JP2005505780 A JP 2005505780A JP 2005505780 A JP2005505780 A JP 2005505780A JP 4464356 B2 JP4464356 B2 JP 4464356B2
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layer
film
heat
white
shrinkable
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JPWO2004094139A1 (en
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幸治 土田
英明 梅田
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Fuji Seal International Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/41—Opaque
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/14—Layer or component removable to expose adhesive
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851—Intermediate layer is discontinuous or differential
    • Y10T428/24868—Translucent outer layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Description

発明の詳細な説明Detailed Description of the Invention

技術分野
本発明は、遮光性を有する熱収縮性乳白フィルム、該熱収縮性乳白フィルムから作製されたシュリンクラベル、及び該ラベルを容器本体に熱収縮により装着したラベル付き容器に関する。 TECHNICAL FIELD The present invention relates to a heat-shrinkable milky white film having a light-shielding property, a shrink label produced from the heat-shrinkable milky-white film, and a labeled container in which the label is attached to a container body by heat shrinking.

背景技術
ビール、清酒、ワイン等のアルコール飲料、緑茶、ビタミン入り飲料などは、光、特に３８０〜５００ｎｍの波長領域の光によって変色や変質が起こりやすい。このような光によって変質しやすい飲料等の容器として、遮光性を付与するために着色されたプラスチックボトルやガラス瓶が広く用いられている。しかし、これらの着色容器は、着色剤を含むため、使用済みの容器を回収・再利用する際に大きな障害となる。 Background Art Alcoholic beverages such as beer, sake, and wine, green tea, and beverages containing vitamins are likely to be discolored or altered by light, particularly light in the wavelength region of 380 to 500 nm. As containers for beverages and the like that are easily altered by light, colored plastic bottles and glass bottles are widely used to impart light shielding properties. However, since these coloring containers contain a colorant, they become a major obstacle when collecting and reusing used containers.

そこで、無色透明なプラスチック製ボトルやガラス瓶を遮光性を付与したシュリンクラベルで容器本体を被覆したラベル付き容器が提案されている。例えば、特開２００２−６８２０２号公報には、酸化亜鉛などの紫外線遮断剤を含有する熱収縮性の合成樹脂フィルムを装着したボトルが開示されている。また、特開２００２−２８５０２０号公報には、特定量の二酸化チタンを含有する白色フィルムから作製された熱収縮性ラベルを装着した容器が開示されている。しかし、これらの容器では、光線透過率、特に可視光線の透過率が比較的高く、遮光性が十分とは言えない。一方、特開２００３−２６２５２号公報には、白色顔料を含有する熱収縮性フィルムのデザインを施す面とは反対側の面に黒色印刷を施したシュリンクラベルが装着された容器が開示されている。しかし、このような容器では、ラベルの内面が黒色であるため、ボトルの口から内容物である乳飲料やビール等の飲料を覗くと、該飲料が黒っぽく見え、見た目の印象が悪く飲食欲が減退しかねない。   In view of this, there has been proposed a labeled container in which a colorless and transparent plastic bottle or glass bottle is covered with a shrink label imparted with light shielding properties. For example, JP-A-2002-68202 discloses a bottle equipped with a heat-shrinkable synthetic resin film containing an ultraviolet blocking agent such as zinc oxide. Japanese Patent Application Laid-Open No. 2002-285020 discloses a container equipped with a heat-shrinkable label produced from a white film containing a specific amount of titanium dioxide. However, these containers have a relatively high light transmittance, particularly visible light transmittance, and are not sufficiently light-shielding. On the other hand, Japanese Patent Application Laid-Open No. 2003-26252 discloses a container in which a shrink label with black printing is attached to a surface opposite to a surface on which a heat shrinkable film containing a white pigment is designed. . However, in such a container, since the inner surface of the label is black, when looking into the contents such as milk drinks and beer such as beer from the mouth of the bottle, the drinks appear black and the appearance is not good and the appetite is not good. It may decline.

発明の開示
従って、本発明の目的は、容器内容物の光による変色や変質を抑制でき、デザイン等の印刷が鮮明で、しかも容器内容物を見たときの印象に優れるラベル付き容器と、このようなラベル付き容器を作製する上で有用な熱収縮性乳白フィルム及びシュリンクラベルを提供することにある。 DISCLOSURE OF THE INVENTION Accordingly, an object of the present invention is to provide a labeled container that can suppress discoloration and deterioration due to light of the container contents, has a clear print such as a design, and has an excellent impression when the container contents are viewed. It is an object of the present invention to provide a heat-shrinkable milky film and a shrink label useful for producing such a labeled container.

本発明者らは、前記目的を達成するため鋭意検討した結果、特定の層構成を有する熱収縮性乳白フィルムを用いたシュリンクラベルで容器本体を被覆すると、容器内の飲料等の光による変質を抑制できると共に、鮮明なデザイン等を施すことができ、しかも容器内容物を見たときの印象に優れ、飲料等が本来の色を損なわず違和感なく見えることを見出し、本発明を完成した。   As a result of intensive investigations to achieve the above object, the present inventors have coated the container body with a shrink label using a heat-shrinkable milky film having a specific layer structure, and the alteration of the beverage in the container due to light. The present invention has been completed by finding that it can be suppressed, can be given a clear design, and has an excellent impression when the contents of the container are viewed, and that beverages and the like can be seen without a sense of discomfort without losing the original color.

すなわち、本発明は、無彩色の中心層と、白色の表裏層とを有する熱収縮性乳白フィルムであって、中心層が黒色着色剤として使用されるカーボンブラックを含み、該カーボンブラックの含有量は中心層全体の０．０１〜３重量％であり、白色の表裏層の各々が独立して白色着色剤として酸化チタンを含み、該酸化チタンの含有量は、各層の総量の１０〜４０重量％であり、該フィルムは、表裏層と中心層とを共押出し成形し、次いで延伸処理することにより形成され、表裏層および中心層の各々が熱収縮性フィルム層であり、該中心層の厚みはフィルム全体の厚みに対して５〜３０％であり、該フィルムは、３８０〜５００ｎｍの波長帯域の光の透過率が５％以下であり、該フィルムの熱収縮率は、９０℃の熱水に１０秒間浸漬したときに一方の方向において２０〜９０％であり、該フィルムの表面の白度が、ＪＩＳ Ｚ ８７１５に準じて測定され、標準白色板の測定値であるＷ値１００に対する相対値として表された場合に、Ｗ値７５以上で表される、熱収縮性乳白フィルムを提供する。
That is, the present invention is a heat-shrinkable milky white film having an achromatic center layer and a white front and back layer, the center layer containing carbon black used as a black colorant, and the content of the carbon black Is 0.01 to 3 wt% of the entire center layer, and each of the white front and back layers independently contains titanium oxide as a white colorant, and the content of the titanium oxide is 10 to 40 wt% of the total amount of each layer The film is formed by co-extrusion of the front and back layers and the center layer, followed by stretching treatment, and each of the front and back layers and the center layer is a heat-shrinkable film layer, and the thickness of the center layer Is 5 to 30% of the thickness of the entire film, the film has a light transmittance of 5% or less in the wavelength band of 380 to 500 nm, and the film has a heat shrinkage ratio of 90 ° C. hot water when immersed for 10 seconds Square and 20-90% in the direction of the white of the surface of the film is measured in accordance with JIS Z 871 5, when expressed as a relative value with respect to the W value 100 is a measure of the standard white plate A heat-shrinkable milky white film represented by a W value of 75 or more is provided.

好ましくは、上記熱収縮性乳白フィルムにおいて、カーボンブラックの含有量は中心層全体の０．１５〜３重量％であり、２００〜６００ｎｍの波長帯域の光の透過率が３％以下である。前記熱収縮性乳白フィルムの他の好ましい態様では、中心層がさらに白色着色剤を含み、該白色着色剤の含有量が中心層全体の１〜４０重量％である。Preferably, in the heat-shrinkable milky white film, the content of carbon black is 0.15 to 3% by weight of the entire central layer, and the light transmittance in the wavelength band of 200 to 600 nm is 3% or less. In another preferred embodiment of the heat-shrinkable milky white film, the center layer further contains a white colorant, and the content of the white colorant is 1 to 40% by weight of the entire center layer.

また、本発明は、３８０〜５００ｎｍの波長帯域の光の透過を抑制する有彩色の中心層と、白色の表裏層とを有する熱収縮性乳白フィルムであって、中心層が有彩色着色剤として黄、赤又は茶系の顔料を少なくとも１種類含み、その含有量が、中心層全体の０．０１〜１重量％であり、白色の表裏層の各々が独立して白色着色剤として酸化チタンを含み、該酸化チタンの含有量は、各層の総量の５〜４０重量％であり、該フィルムは、表裏層と中心層とを共押出し成形し、次いで延伸処理することにより形成され、表裏層および中心層の各々が熱収縮性フィルム層であり、該中心層の厚みはフィルム全体の厚みに対して５〜３０％であり、該フィルムは、３８０〜５００ｎｍの波長帯域の光の透過率が５％以下であり、該フィルムの熱収縮率は、９０℃の熱水に１０秒間浸漬したときに一方の方向において２０〜９０％であり、該フィルムの表面の白度が、ＪＩＳ Ｚ ８７１５に準じて測定され、標準白色板の測定値であるＷ値１００に対する相対値として表された場合に、Ｗ値７５以上で表される、熱収縮性乳白フィルムを提供する。
The present invention is also a heat-shrinkable milky white film having a chromatic color center layer that suppresses transmission of light in the wavelength band of 380 to 500 nm and a white front and back layer, and the center layer is a chromatic colorant. It contains at least one kind of yellow, red or brown pigment, its content is 0.01 to 1 % by weight of the entire center layer, and each of the white front and back layers independently contains titanium oxide as a white colorant. And the content of the titanium oxide is 5 to 40% by weight of the total amount of each layer, and the film is formed by co-extrusion of the front and back layers and the center layer, followed by stretching, Each of the central layers is a heat-shrinkable film layer, and the thickness of the central layer is 5 to 30% with respect to the total thickness of the film, and the film has a light transmittance of 5 to 380 to 500 nm. %, And the heat shrinkage rate of the film Is 20 to 90% in the one direction when immersed for 10 seconds at 90 ° C. hot water, white of the surface of the film is measured in accordance with JIS Z 871 5, measured values of the standard white plate When expressed as a relative value with respect to a W value of 100, a heat-shrinkable milky film represented by a W value of 75 or more is provided.

好ましくは、上記熱収縮性乳白フィルムにおいて、中心層がさらに白色着色剤を含み、白色着色剤の含有量が中心層全体の０．１〜４０重量％である。 Preferably, in the above heat-shrinkable milky film, centered layer further comprises a white colorant, the amount of the white colorant is 0.1 to 40 wt% of the total center layer.

本発明は、また、上記熱収縮性乳白フィルムおよび該フィルムの表層側の表面に表示印刷インキ層を有するシュリンクラベルを提供する。   The present invention also provides the heat-shrinkable milky film and a shrink label having a display printing ink layer on the surface on the surface side of the film.

本発明は、さらに、容器本体に上記のシュリンクラベルを装着したラベル付き容器を提供する。   The present invention further provides a labeled container in which the above-described shrink label is attached to the container body.

図面の簡単な説明
第１図は本発明のシュリンクラベルの一例を示す概略断面図である。
第２図は実施例２，３，４及び比較例１で得られた熱収縮性フィルムの光線透過率（透過度）を示すグラフである。
第３図は比較例３、実施例１１〜１３で得られた熱収縮性フィルムの光線透過率（透過度）を示すグラフである。
第４図は比較例７、実施例１８〜２２で得られた熱収縮性フィルムの光線透過率（透過度）を示すグラフである。 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic sectional view showing an example of a shrink label of the present invention.
FIG. 2 is a graph showing the light transmittance (transmittance) of the heat-shrinkable films obtained in Examples 2, 3, 4 and Comparative Example 1.
FIG. 3 is a graph showing the light transmittance (transmittance) of the heat-shrinkable films obtained in Comparative Example 3 and Examples 11-13.
FIG. 4 is a graph showing the light transmittance (transmittance) of the heat-shrinkable films obtained in Comparative Example 7 and Examples 18-22.

発明を実施するための最良の形態
以下、本発明を、必要に応じて図面を参照しつつ詳細に説明する。本発明の熱収縮性乳白フィルムは、無彩色又は３８０〜５００ｎｍの波長帯域の光の透過を抑制する有彩色の中心層と白色の表裏層（表層及び裏層）とを有している。なお、表層とは容器へ装着したときに外面側となり、ラベルを作製する際にデザイン等の印刷を施す側の層を意味し、裏層とはラベルとした際の容器側の層を意味する。本発明の熱収縮性乳白フィルムでは、中心層が、無彩色であるか又は３８０〜５００ｎｍの波長帯域（紫外線域〜青緑色の可視光域）の光に対して遮光性を有しているため、ビタミン入り飲料やビール等の容器内容物の変色や変質を抑制又は防止できる。また、表層が白色であるため乳白色を呈し、ラベルを作製する際にデザイン等を鮮明に印刷することができる。さらに、裏層が白色であるため、該ラベルを容器に装着してラベル付き容器とした際、容器の口から内容物を見ると容器内の飲料等の内容物が本来の色が損なわれることなく自然に見える。熱収縮性乳白フィルムは、熱収縮性や美粧性、取扱性等を損なわない範囲で、前記中心層及び表裏層以外の層（透明な樹脂層、他の着色樹脂層、層間の接着性を向上させるための樹脂層など）を有していてもよい。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the drawings as necessary. The heat-shrinkable milky film of the present invention has an achromatic color or a chromatic color central layer that suppresses transmission of light in the wavelength band of 380 to 500 nm and a white front and back layer (surface layer and back layer). The surface layer is the outer surface side when attached to the container, means the layer on the side where the design is printed when producing a label, and the back layer means the layer on the container side when used as a label. . In the heat-shrinkable milky white film of the present invention, the center layer has an achromatic color or has a light shielding property against light in a wavelength band of 380 to 500 nm (ultraviolet region to blue-green visible light region). Discoloration and alteration of container contents such as beverages containing vitamins and beer can be suppressed or prevented. In addition, since the surface layer is white, it is milky white and the design and the like can be printed clearly when producing a label. Furthermore, since the back layer is white, when the label is attached to the container to make a labeled container, the original color of the contents such as beverages in the container is impaired when the contents are viewed from the mouth of the container. It looks natural. Heat-shrinkable milky white film is a layer other than the center layer and front and back layers (transparent resin layer, other colored resin layers, and improved adhesion between layers as long as it does not impair heat-shrinkability, cosmetics, handleability, etc. For example, a resin layer).

本発明のシュリンクラベルは前記熱収縮性乳白フィルムの表層側の面に表示印刷インキ層を有している。図１は本発明のシュリンクラベルの一例を示す概略断面図である。このシュリンクラベルの例では、白色の表層１と、無彩色又は３８０〜５００ｎｍの波長帯域の光の透過を抑制しうる有彩色の中心層２と、白色の裏層３とからなる熱収縮性乳白フィルム４の表層１側の表面に表示印刷インキ層５が形成されている。   The shrink label of the present invention has a display printing ink layer on the surface side of the heat-shrinkable milky film. FIG. 1 is a schematic sectional view showing an example of the shrink label of the present invention. In this example of a shrink label, a heat-shrinkable milky white comprising a white surface layer 1, a chromatic color central layer 2 capable of suppressing transmission of light in an achromatic or 380 to 500 nm wavelength band, and a white back layer 3. A display printing ink layer 5 is formed on the surface of the film 4 on the surface layer 1 side.

表層１、中心層２及び裏層３は、それぞれ、熱収縮性フィルム層で構成することができる。熱収縮性フィルム層の素材としては、熱収縮性フィルムの材料として通常用いられているものを使用でき、例えば、ポリエステル系樹脂、ポリスチレン系樹脂、ポリオレフィン系樹脂、ポリ塩化ビニル樹脂などが挙げられる。これらの素材は単独で又は２種以上混合して使用できる。   The surface layer 1, the center layer 2, and the back layer 3 can each be comprised with a heat-shrinkable film layer. As the material of the heat-shrinkable film layer, those usually used as the material of the heat-shrinkable film can be used, and examples thereof include polyester resins, polystyrene resins, polyolefin resins, and polyvinyl chloride resins. These materials can be used alone or in admixture of two or more.

前記ポリエステル系樹脂としてはジオール成分とジカルボン酸成分（又はそのエステル等の反応性誘導体）との縮合等の公知の方法により得られるポリエステル系樹脂を使用できる。ポリエステル系樹脂を構成するジオール成分としては、例えば、エチレングリコール、プロピレングリコール、１，３−プロパンジオール、２，２−ジメチル−１，３−プロパンジオール、２−メチル−２−エチル−１，３−プロパンジオール、２，２−ジエチル−１，３−プロパンジオール、２−エチル−２−ブチル−１，３−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、２，２，４−トリメチル−１，６−ヘキサンジオール等の脂肪族ジオール；チオジエタノール；ジエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコール；１，２−シクロヘキサンジメタノール、１，３−シクロヘキサンジメタノール、１，４−シクロヘキサンジメタノール等の脂環式ジオール；２，２−ビス（４′−β−ヒドロキシエトキシジフェニル）プロパン、ビス（４′−β−ヒドロキシエトキシフェニル）スルホン等のビスフェノール系化合物のエチレンオキサイド付加物、キシリレングリコール等の芳香族ジオールなどが挙げられる。これらのジオール成分は単独で又は２種以上を組み合わせて使用できる。   As the polyester resin, a polyester resin obtained by a known method such as condensation of a diol component and a dicarboxylic acid component (or a reactive derivative such as an ester thereof) can be used. Examples of the diol component constituting the polyester resin include ethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 2-methyl-2-ethyl-1,3. -Propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6- Aliphatic diols such as hexanediol and 2,2,4-trimethyl-1,6-hexanediol; thiodiethanol; polyalkylene glycols such as diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; 1,2-cyclohexanedimethanol 1,3-cyclohexanedimethanone Alicyclic diols such as 1,4-cyclohexanedimethanol; bisphenol compounds such as 2,2-bis (4′-β-hydroxyethoxydiphenyl) propane and bis (4′-β-hydroxyethoxyphenyl) sulfone Examples include ethylene oxide adducts and aromatic diols such as xylylene glycol. These diol components can be used alone or in combination of two or more.

ポリエステル系樹脂を構成するジカルボン酸成分としては、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の脂肪族ジカルボン酸；１，４−デカヒドロナフタレンジカルボン酸、１，５−デカヒドロナフタレンジカルボン酸、２，６−デカヒドロナフタレンジカルボン酸、１，３−シクロヘキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸等の脂環式ジカルボン酸；テレフタル酸、イソフタル酸、４，４′−ビフェニルジカルボン酸、トランス−３，３′−スチルベンジカルボン酸、トランス−４，４′−スチルベンジカルボン酸、４，４′−ジベンジルジカルボン酸、２，６−ナフタレンジカルボン酸などのナフタレンジカルボン酸類等の芳香族ジカルボン酸などが挙げられる。これらのジカルボン酸成分は単独で又は２種以上を組み合わせて使用できる。   Examples of the dicarboxylic acid component constituting the polyester resin include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; -Alicyclic dicarboxylic acids such as decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid; Terephthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid, trans-3,3'-stilbene dicarboxylic acid, trans-4,4'-stilbene dicarboxylic acid, 4,4'-dibenzyldicarboxylic acid, 2,6 -Aromatic dica such as naphthalene dicarboxylic acids such as naphthalene dicarboxylic acid Such as Bon acid, and the like. These dicarboxylic acid components can be used alone or in combination of two or more.

ポリエステル系樹脂としては、主ジオール成分としてエチレングリコール、主ジカルボン酸成分としてテレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸を用いて得られるポリエステル系樹脂が特に好ましい。   The polyester resin is particularly preferably a polyester resin obtained using ethylene glycol as the main diol component and aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid as the main dicarboxylic acid component.

前記ポリスチレン系樹脂としては、スチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体等のスチレン−共役ジエンブロック共重合体や、該スチレン−共役ジエンブロック共重合体に、ポリスチレン、スチレンと（メタ）アクリル酸エステル等のアクリル系単量体との共重合体などの他のポリマーを混合したものなどを使用できる。前記スチレン−共役ジエンブロック共重合体において、スチレン含有量は３０〜９５重量％程度、共役ジエン含有量は５〜７０重量％程度である。   Examples of the polystyrene resin include styrene-conjugated diene block copolymers such as styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, and polystyrene-conjugated diene block copolymers such as styrene-conjugated diene block copolymers. A mixture of other polymers such as a copolymer of styrene and an acrylic monomer such as (meth) acrylic acid ester can be used. In the styrene-conjugated diene block copolymer, the styrene content is about 30 to 95% by weight, and the conjugated diene content is about 5 to 70% by weight.

白色の表層１及び裏層３は、それぞれ、前記樹脂成分と白色着色剤とで構成できる。白色着色剤としては、特に限定されず、例えば、酸化チタン、アンチモン白、硫化亜鉛、亜鉛華などの白色顔料等を使用できる。これらの中でも、酸化チタンは白度が高く、中心層２の有彩色が透けて見えにくいため特に好ましい。表層１及び裏層３における白色着色剤の添加量は、白度やコスト等を考慮して適宜選択でき、その種類によっても異なるが、各層につき、全体の１〜２０体積％程度、例えば酸化チタンの場合には、各層につき、全体の５〜４０重量％程度、好ましくは１０〜２５重量％程度である。   The white surface layer 1 and the back layer 3 can be composed of the resin component and the white colorant, respectively. The white colorant is not particularly limited, and for example, white pigments such as titanium oxide, antimony white, zinc sulfide, and zinc white can be used. Among these, titanium oxide is particularly preferable because it has high whiteness and the chromatic color of the center layer 2 is difficult to see through. The addition amount of the white colorant in the surface layer 1 and the back layer 3 can be appropriately selected in consideration of whiteness, cost, etc., and varies depending on the type, but about 1 to 20% by volume of each layer, for example, titanium oxide In this case, the total amount of each layer is about 5 to 40% by weight, preferably about 10 to 25% by weight.

白色着色剤として酸化チタン等の白色顔料を用いる場合、その平均粒子径は、例えば０．０１〜１０μｍ、好ましくは０．０１〜５μｍ、より好ましくは０．１〜１μｍ程度である。平均粒子径が０．０１μｍ未満では分散性が悪くなり、１０μｍを超えるとフィルム表面が粗くなり、外観が悪くなりやすい。   When a white pigment such as titanium oxide is used as the white colorant, the average particle size is, for example, 0.01 to 10 μm, preferably 0.01 to 5 μm, and more preferably about 0.1 to 1 μm. When the average particle size is less than 0.01 μm, the dispersibility is deteriorated, and when it exceeds 10 μm, the film surface becomes rough and the appearance tends to be deteriorated.

白色の表層１に青色着色剤（青色顔料等）を少量添加すると、中心層の黄、赤、茶色が表から目立たなくなる。青色着色料の添加量は、例えば表層１全体の０．０１〜０．５重量％程度である。   When a small amount of a blue colorant (blue pigment or the like) is added to the white surface layer 1, the yellow, red and brown of the center layer will not be noticeable from the surface. The amount of blue colorant added is, for example, about 0.01 to 0.5% by weight of the entire surface layer 1.

なお、白色の表層１及び裏層３には、前記白色着色剤により着色された層のほか、発泡や、相溶性の悪い樹脂を２種類以上混ぜる等によって白色、白濁色又は乳白色を呈する層も含む。   In addition, the white surface layer 1 and the back layer 3 include a layer colored with the white colorant, and a layer exhibiting white, cloudy or milky white by foaming or mixing two or more resins having poor compatibility. Including.

中心層２には、無彩色の層が含まれ、具体的には、黒色の中心層及びグレー系の中心層等が含まれる。前記黒色の中心層２は、前記樹脂成分と黒色着色剤とで構成できる。黒色着色剤としては、特に限定されず、公知の黒色顔料等の何れも使用できるが、それらの中でもカーボンブラックが特に好ましい。黒色の中心層２における黒色着色剤の添加量は、フィルム表裏層の白度を損なわない範囲で、遮光性やコスト等を考慮して適宜選択できるが、通常、中心層２全体に対して１×１０-3〜６体積％であるのが好ましい。 The center layer 2 includes an achromatic layer, and specifically includes a black center layer and a gray-based center layer. The black center layer 2 can be composed of the resin component and a black colorant. The black colorant is not particularly limited, and any known black pigment or the like can be used. Among them, carbon black is particularly preferable. The addition amount of the black colorant in the black center layer 2 can be appropriately selected in consideration of light shielding properties, cost, etc. as long as the whiteness of the film front and back layers is not impaired. It is preferable that it is * 10 < -3 > -6 volume%.

黒色着色剤としてカーボンブラックを用いる場合、その添加量は、通常、中心層２全体の０．０１〜５重量％、好ましくは０．０５〜３重量％程度である。また、カーボンブラックの添加量は、熱収縮性乳白フィルム全体に対して５×１０-4重量％以上（例えば、５×１０-4〜２．５重量％程度）であるのが好ましい。さらに、カーボンブラックの乳白フィルム単位面積当たりの含有量としては、１×１０-4ｇ／ｍ2〜５ｇ／ｍ2が好ましく、さらに好ましくは１×１０-3ｇ／ｍ2〜１ｇ／ｍ2程度である。 When carbon black is used as the black colorant, the amount added is usually 0.01 to 5% by weight, preferably about 0.05 to 3% by weight, based on the entire center layer 2. The amount of carbon black added is preferably 5 × 10 −4 wt% or more (for example, about 5 × 10 −4 to 2.5 wt%) with respect to the entire heat-shrinkable milky white film. Further, as the content per milky film unit area of the carbon black, 1 × 10 -4 g / m 2 ~5g / m 2 are preferred, more preferably 1 × 10 -3 g / m 2 ~1g / m 2 Degree.

黒色着色剤としてカーボンブラック等の黒色顔料を用いる場合、その平均粒子径は、例えば０．００１〜１０μｍ、好ましくは０．０１〜１μｍ程度である。平均粒子径が０．００１μｍ未満の場合には分散性が低下しやすく、１０μｍを超えると十分な遮光性が得られにくくなる。   When a black pigment such as carbon black is used as the black colorant, the average particle diameter is, for example, about 0.001 to 10 μm, preferably about 0.01 to 1 μm. When the average particle size is less than 0.001 μm, the dispersibility tends to be lowered, and when it exceeds 10 μm, it is difficult to obtain sufficient light shielding properties.

前記グレー系の中心層２は、前記樹脂成分、黒色着色剤、及び白色着色剤で構成できる。黒色着色剤及び白色着色剤としては前記のものを使用できる。特に、黒色着色剤としてはカーボンブラックが好ましく、白色着色剤としては酸化チタンが好ましく用いられる。中心層２における黒色着色剤の添加量及び平均粒子径は前記と同様である。白色着色剤の添加量は、フィルムの白度、遮光性やコスト等を考慮して適宜選択できるが、通常、中心層２全体の１〜４０重量％、好ましくは５〜２５重量％程度である。   The gray-based center layer 2 can be composed of the resin component, a black colorant, and a white colorant. As the black colorant and the white colorant, those described above can be used. In particular, carbon black is preferable as the black colorant, and titanium oxide is preferably used as the white colorant. The addition amount and average particle diameter of the black colorant in the center layer 2 are the same as described above. The addition amount of the white colorant can be appropriately selected in consideration of the whiteness of the film, light-shielding properties, cost, etc., but is usually about 1 to 40% by weight, preferably about 5 to 25% by weight of the entire center layer 2. .

なお、無彩色の中心層は、着色剤としてアルミ微粒子、銀微粉末などの金属微粒子が添加されたシルバー等のメタリック調の色の層であってもよい。   The achromatic center layer may be a metallic color layer such as silver to which metal fine particles such as aluminum fine particles and silver fine powder are added as a colorant.

中心層２は、上記の他に、前記樹脂成分と３８０〜５００ｎｍの波長帯域の光の透過を抑制しうる有彩色着色剤とで構成することもできる。該有彩色着色剤としては、黄系顔料、赤系顔料、茶系顔料などを使用できる。黄系顔料としては、例えば、イエローオーカー、オーレオリン、カドミウムイエロー、カドミウムオレンジ、クロムイエロー、ジンクイエロー、ネイプルスイエロー、ニッケルイエローなどの無機顔料；アゾ系顔料、グリニッシュイエローなどの有機顔料が例示される。赤系顔料としては、例えば、カドミウムレッド、カドモポンレッド、クロムレッド、バーミリオン、ベンガラなどの無機顔料；アゾ系顔料、アリザリンレーキ、キナクリドン、コチニールレーキペリレンなどの有機顔料が挙げられる。茶系顔料としては、例えば、アンバー、ローアンバー、バーントアンバー、イエローオーカー、ヴァンダイクブラウン、シェンナ、ローシェンナ、バーントシェンナ、ベンガラなどの無機顔料；セピアなどの有機顔料が例示される。有彩色着色剤は単独で又は２種以上を組み合わせて使用できる。また、３８０〜５００ｎｍの波長帯域の光の透過を抑制する有彩色の中心層は、着色剤としての金属微粒子が添加されたメタリック調の色の層であってもよい。   In addition to the above, the center layer 2 can also be composed of the resin component and a chromatic colorant capable of suppressing transmission of light in the wavelength band of 380 to 500 nm. As the chromatic colorant, yellow pigments, red pigments, brown pigments and the like can be used. Examples of yellow pigments include inorganic pigments such as yellow ocher, aureolin, cadmium yellow, cadmium orange, chrome yellow, zinc yellow, naples yellow, and nickel yellow; and organic pigments such as azo pigments and greenish yellow The Examples of red pigments include inorganic pigments such as cadmium red, cadmopon red, chrome red, vermilion, and bengara; organic pigments such as azo pigments, alizarin lake, quinacridone, and cochineal lake perylene. Examples of tea pigments include inorganic pigments such as amber, low amber, burnt amber, yellow ocher, van dyke brown, shenna, roshenna, burnt shenna, bengara, and organic pigments such as sepia. The chromatic colorants can be used alone or in combination of two or more. The chromatic color central layer that suppresses transmission of light in the wavelength band of 380 to 500 nm may be a metallic color layer to which metal fine particles as a colorant are added.

中心層２における有彩色着色剤の添加量は、フィルム表裏層の白度を損なわない範囲で、遮光性やコスト等を考慮して適宜選択できるが、通常、中心層２全体の０．０１〜２０重量％、好ましくは０．０５〜１５重量％程度である。また、有彩色着色剤の添加量は、熱収縮性乳白フィルム全体に対して５×１０-4重量％以上（例えば、５×１０-4〜５重量％程度）であるのが好ましい。さらに、有彩色着色剤の乳白フィルム単位面積当たりの含有量としては１×１０-4ｇ／ｍ2〜５ｇ／ｍ2が好ましく、さらに好ましくは１×１０-3ｇ／ｍ2〜１ｇ／ｍ2程度である。 The addition amount of the chromatic colorant in the center layer 2 can be appropriately selected in consideration of light shielding properties, cost, etc., as long as the whiteness of the film front and back layers is not impaired. It is about 20% by weight, preferably about 0.05 to 15% by weight. Moreover, it is preferable that the addition amount of a chromatic colorant is 5 * 10 < -4 > weight% or more (for example, about 5 * 10 < -4 > -5 weight%) with respect to the whole heat-shrinkable milky white film. Further, preferably 1 × 10 -4 g / m 2 ~5g / m 2 as content per milky film unit area of chromatic coloring agent, more preferably 1 × 10 -3 g / m 2 ~1g / m It is about 2 .

有彩色着色剤の平均粒子径は、該着色剤の種類によっても異なるが、通常０．０１〜１μｍ程度である。平均粒子径が１μｍより大きいと十分な遮光性が得られにくくなり、０．０１μｍ未満では分散性が低下しやすい。着色剤が黄系顔料の場合は、平均粒子径は０．３〜０．６μｍの範囲が特に好ましく、着色剤が茶系顔料の場合は、平均粒子径は０．４〜０．７μｍの範囲が特に好ましい。   The average particle diameter of the chromatic colorant varies depending on the type of the colorant, but is usually about 0.01 to 1 μm. When the average particle diameter is larger than 1 μm, it is difficult to obtain sufficient light shielding properties, and when it is less than 0.01 μm, the dispersibility tends to be lowered. When the colorant is a yellow pigment, the average particle size is particularly preferably in the range of 0.3 to 0.6 μm. When the colorant is a tea pigment, the average particle size is in the range of 0.4 to 0.7 μm. Is particularly preferred.

中心層２には白さを増すため白色着色剤（白色顔料等）を添加してもよい。有彩色着色剤として赤系顔料や茶系顔料を用いた場合には、表面の外観に中心層２の有彩色が僅かに認められることがあるが、中心層２に白色着色剤を添加することにより、中心層２の有彩色をほぼ完全に隠蔽することが可能となる。白色着色剤としては前記のものを使用でき、特に酸化チタンが好適である。白色着色剤を添加する際の添加量は、例えば中心層２全体の０．１〜４０重量％、好ましくは５〜２５重量％程度である。   A white colorant (white pigment or the like) may be added to the center layer 2 to increase whiteness. When a red pigment or a brown pigment is used as the chromatic colorant, a slight chromatic color of the center layer 2 may be recognized on the surface appearance, but a white colorant should be added to the center layer 2 Thus, the chromatic color of the center layer 2 can be almost completely hidden. As the white colorant, those described above can be used, and titanium oxide is particularly preferable. The amount of white colorant added is, for example, about 0.1 to 40% by weight, preferably about 5 to 25% by weight, based on the entire center layer 2.

中心層２は、構成する樹脂素材として必ずしも透明な素材を用いる必要はない。従って、該樹脂素材として、印刷不良のフィルム、フィルム周縁部の耳の部分、印刷の残っているフィルム断片などのリサイクル材料を有効に使用でき、経済的に極めて有利である。この場合、リサイクル材料の使用割合は、遮光性や熱収縮性等の特性を損なわない範囲で適宜選択できるが、一般には、全層を構成する樹脂素材全量に対して３０重量％以下（例えば１〜３０重量％程度）であるのが好ましい。   The center layer 2 does not necessarily need to use a transparent material as a constituent resin material. Therefore, as the resin material, recycled materials such as a poorly printed film, an edge portion of the peripheral edge of the film, and a film piece that remains printed can be effectively used, which is extremely advantageous economically. In this case, the use ratio of the recycled material can be appropriately selected within a range that does not impair the properties such as light-shielding properties and heat-shrinkability, but generally 30% by weight or less (for example, 1) About 30% by weight).

本発明では、熱収縮性乳白フィルム４においては、熱収縮性乳白フィルム全体として熱収縮性を有していればよく、必ずしも表層１、中心層２及び裏層３の全てを熱収縮性フィルム層で構成する必要はない。例えば、前記３層のうち１層又は２層を熱収縮性フィルム層で構成したり、或いは前記３層以外の他の層として熱収縮性フィルム層を設けることにより、乳白フィルム４に熱収縮性を付与することもできる。表層１、中心層２、裏層３は、熱収縮性フィルム層で構成する以外に、それぞれ、印刷層（又はコーティング層）で構成することができる。例えば、表層１、裏層３は、酸化チタン等の白色顔料を含むインキを用いて、グラビア印刷等の公知の印刷法で、中心層２となる無彩色又は有彩色の熱収縮性フィルム層の表裏両面に印刷を施すことにより形成できる。また、中心層２は、無彩色又は有彩色着色剤を含むインキを用いて、同じくグラビア印刷等の公知の印刷法で、表層１となる白色の熱収縮性フィルム層に印刷を施すことにより形成できる。なお、熱収縮性フィルム層を２層以上設ける場合、それらを構成する樹脂は互いに異種のものであってもよいが、作業性やリサイクル性等の点から同種のものであるのが好ましい。   In the present invention, the heat-shrinkable milky film 4 only needs to have heat-shrinkability as a whole heat-shrinkable milky film, and all of the surface layer 1, the center layer 2 and the back layer 3 are not necessarily heat-shrinkable film layers. It is not necessary to configure with. For example, one or two of the three layers are composed of a heat-shrinkable film layer, or a heat-shrinkable film layer is provided as a layer other than the three layers, whereby the milky film 4 is heat-shrinkable. Can also be given. The surface layer 1, the center layer 2, and the back layer 3 can each be composed of a print layer (or coating layer) in addition to being composed of a heat-shrinkable film layer. For example, the surface layer 1 and the back layer 3 are made of an achromatic or chromatic heat-shrinkable film layer that becomes the center layer 2 by a known printing method such as gravure printing using an ink containing a white pigment such as titanium oxide. It can be formed by printing on both front and back sides. The center layer 2 is formed by printing on the white heat-shrinkable film layer that becomes the surface layer 1 by a known printing method such as gravure printing, using an ink containing an achromatic or chromatic colorant. it can. When two or more heat-shrinkable film layers are provided, the resins constituting them may be different from each other, but are preferably the same from the viewpoint of workability and recyclability.

熱収縮性乳白フィルム４の代表的な層構成として、（１）白色の熱収縮性フィルム層（表層）／黒色、グレー系又は有彩色の熱収縮性フィルム層（中心層）／白色の熱収縮性フィルム層（裏層）、（２）白色の熱収縮性フィルム層（表層）／黒色、グレー系又は有彩色の熱収縮性フィルム層（中心層）／白色の印刷層（裏層）、（３）白色の印刷層（表層）／黒色、グレー系又は有彩色の熱収縮性フィルム層（中心層）／白色の熱収縮性フィルム層（裏層）などが挙げられる。本発明では、無彩色又は有彩色の着色剤を直接樹脂に練り込み、濃度を得ることができるなど、コストを低減できることから、少なくとも中心層２が黒色、グレー系又は有彩色の熱収縮性フィルム層である層構成が好ましい。無彩色又は有彩色の中心層にはリサイクル材料を利用することもでき、特に黒色の中心層にはリサイクル材料をより多く利用することができる。また、（ｉ）後述のように３層を共押出しという簡易な手段で形成でき、押出し後、該３層に同時に延伸処理を施して熱収縮性を付与できるので生産効率よく熱収縮性乳白フィルムを製造できること、（ii）グラビア印刷等の印刷手段を採用する場合には、インキ中の溶剤によって熱収縮性フィルム層が侵されたり白色の濃度を高くすることが困難であったり、一般にコストが高くなること、及び（iii）印刷層の場合には高収縮時にインキ割れを起こして見栄えが悪くなる可能性があること等の理由から、表層１、中心層２及び裏層３の全てを熱収縮性フィルム層で構成するのが好ましい。   As a typical layer structure of the heat-shrinkable milky white film 4, (1) white heat-shrinkable film layer (surface layer) / black, gray or chromatic color heat-shrinkable film layer (center layer) / white heat-shrinkable Film layer (back layer), (2) white heat-shrinkable film layer (surface layer) / black, gray or chromatic color heat-shrinkable film layer (center layer) / white print layer (back layer), ( 3) White printed layer (surface layer) / black, gray or chromatic color heat-shrinkable film layer (center layer) / white heat-shrinkable film layer (back layer). In the present invention, since an achromatic or chromatic colorant can be directly kneaded into a resin to obtain a concentration and the cost can be reduced, at least the central layer 2 is a black, gray or chromatic color heat-shrinkable film. The layer structure which is a layer is preferable. A recycled material can also be used for the achromatic or chromatic center layer, and more of the recycled material can be used particularly for the black center layer. Further, (i) as described later, the three layers can be formed by a simple means of co-extrusion, and after the extrusion, the three layers can be simultaneously stretched to impart heat shrinkability, so that heat shrinkable milky film can be produced with high production efficiency. (Ii) When adopting printing means such as gravure printing, the heat-shrinkable film layer is eroded by the solvent in the ink or it is difficult to increase the white density, and the cost is generally low. The surface layer 1, the center layer 2 and the back layer 3 are all heated for reasons such as high and (iii) in the case of the printing layer, there is a possibility that the ink crack will occur at the time of high shrinkage and the appearance may deteriorate. It is preferable to comprise a shrinkable film layer.

熱収縮性乳白フィルム４を構成する表層１、中心層２及び裏層３は、それぞれ、必要に応じて添加剤を含んでいてもよい。このような添加剤として、例えば、滑剤、充填剤、熱安定剤、酸化防止剤、紫外線吸収剤、帯電防止剤、難燃剤などが挙げられる。   The surface layer 1, the center layer 2, and the back layer 3 which comprise the heat-shrinkable milky film 4 may each contain the additive as needed. Examples of such additives include lubricants, fillers, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, and the like.

熱収縮性乳白フィルム４の厚みは、取扱性、外観、遮光性、熱収縮性等の特性を損なわない範囲で適宜設定でき、例えば１０〜２００μｍ、好ましくは３０〜７０μｍ程度である。このうち、中心層２の厚みは、一般に、熱収縮性乳白フィルム４全体の厚みの１〜８０％程度、好ましくは５〜５０％、特に５〜３０％程度である。   The thickness of the heat-shrinkable milky film 4 can be set as appropriate as long as the properties such as handleability, appearance, light-shielding property, and heat-shrinkability are not impaired, and are, for example, about 10 to 200 μm, preferably about 30 to 70 μm. Among these, the thickness of the center layer 2 is generally about 1 to 80%, preferably 5 to 50%, particularly about 5 to 30% of the total thickness of the heat-shrinkable milky film 4.

熱収縮性乳白フィルム４は、積層フィルムを製造する際の慣用の方法、例えば、共押出し法、ラミネート法等により製造できる。より具体的には、例えば、前記（１）白色の熱収縮性フィルム層（表層）／黒色、グレー系又は有彩色の熱収縮性フィルム層（中心層）／白色の熱収縮性フィルム層（裏層）の層構成を有する熱収縮性乳白フィルムは、樹脂及び白色着色剤を含む樹脂組成物（Ａ）と、樹脂及び黒色着色剤又は有彩色着色剤を少なくとも含む樹脂組成物（Ｂ）と、樹脂及び白色着色剤を含む樹脂組成物（Ｃ）とを、Ｔダイ又は環状ダイを備えた押出機を用いて溶融共押出し成形し、冷却ロール等により冷却した後、延伸処理することにより製造できる。延伸はテンター方式、チューブ方式の何れの方式で行うこともできる。延伸は一軸延伸であっても二軸延伸であってもよい。延伸倍率は所望する熱収縮率に応じて適宜設定できる。このように、共押出し法により成形した後、延伸する方法は、積層が容易でしかも各層を同じ条件で延伸することができるため好ましい方法である。なお、表層と裏層をそれぞれ２層構成とした５層構成の溶融共押出しでも良い。   The heat-shrinkable milky white film 4 can be produced by a conventional method for producing a laminated film, such as a coextrusion method or a laminating method. More specifically, for example, (1) white heat-shrinkable film layer (surface layer) / black, gray or chromatic heat-shrinkable film layer (center layer) / white heat-shrinkable film layer (back The heat-shrinkable milky white film having the layer structure of (layer) includes a resin composition (A) containing a resin and a white colorant, and a resin composition (B) containing at least a resin and a black colorant or a chromatic colorant, The resin composition (C) containing a resin and a white colorant can be produced by melt-coextrusion using an extruder equipped with a T die or an annular die, cooling with a cooling roll, etc., and then stretching. . Stretching can be performed by either a tenter method or a tube method. The stretching may be uniaxial stretching or biaxial stretching. The draw ratio can be appropriately set according to the desired heat shrinkage rate. Thus, the method of stretching after molding by the coextrusion method is a preferable method because lamination is easy and each layer can be stretched under the same conditions. Note that a melt coextrusion having a five-layer structure in which the surface layer and the back layer each have a two-layer structure may be used.

また、前記（１）の層構成を有する熱収縮性乳白フィルムは、各層の熱収縮性フィルムを別々の工程で押出し成形した後に延伸加工して作製し、これらをドライラミネート法により積層して製造することもできる。なお、この場合は、各層の間に接着剤層を有するため、上記共押出し層に比べ収縮性を阻害するが、共押出しが困難な樹脂からなるフィルムを積層することができる。   Further, the heat-shrinkable milky white film having the layer structure of (1) is produced by extruding the heat-shrinkable film of each layer in a separate step and then drawing and laminating them by a dry laminating method. You can also In this case, since an adhesive layer is provided between the layers, a film made of a resin that inhibits shrinkage compared to the coextruded layer but is difficult to coextrude can be laminated.

前記（２）白色の熱収縮性フィルム層（表層）／黒色、グレー系又は有彩色の熱収縮性フィルム層（中心層）／白色の印刷層（裏層）の層構成を有する熱収縮性乳白フィルムは、樹脂及び白色着色剤を含む樹脂組成物（Ａ）と、樹脂及び黒色着色剤又は有彩色着色剤を少なくとも含む樹脂組成物（Ｂ）とを、Ｔダイ又は環状ダイを備えた押出機を用いて溶融共押出し成形し、冷却ロール等により冷却した後、上記と同様の延伸処理を施し、次いで前記樹脂組成物（Ｂ）により形成された層（中心層に相当）の裏面側に、白色インキを用いたグラビア印刷等により白色印刷を１層又は複層施すことにより製造できる。このように裏層にグラビア印刷等により白色印刷層を形成した場合には、白色インキに滑剤等を添加して裏層の表面の滑り性を高めることができる等の利点がある。   (2) Heat-shrinkable milky layer having a layer structure of white heat-shrinkable film layer (surface layer) / black, gray or chromatic color heat-shrinkable film layer (center layer) / white printed layer (back layer) The film includes a resin composition (A) containing a resin and a white colorant, and a resin composition (B) containing at least a resin and a black colorant or a chromatic colorant, and an extruder provided with a T die or an annular die. After being subjected to melt coextrusion molding and cooling with a cooling roll or the like, the same stretching treatment as described above is performed, and then on the back side of the layer formed by the resin composition (B) (corresponding to the center layer), It can be produced by applying a single layer or multiple layers of white printing by gravure printing using a white ink. Thus, when a white printed layer is formed on the back layer by gravure printing or the like, there is an advantage that the slipperiness of the surface of the back layer can be increased by adding a lubricant or the like to the white ink.

熱収縮性乳白フィルム４の熱収縮率は、被着物である容器等の形状等に応じて適宜設定できるが、通常、少なくとも一方の方向に１５％以上である。例えば、一軸延伸フィルムの場合の熱収縮率は、９０℃の熱水に１０秒間浸漬処理した時、主延伸方向において、通常２０〜９０％、好ましくは３０〜７０％程度である。また、二軸延伸フィルムの場合の熱収縮率は、９０℃の熱水に１０秒間浸漬処理した時、一方の方向（例えば幅方向）において、通常２０〜９０％、好ましくは３０〜７０％程度であり、他方の方向（例えば長さ方向）において、通常１〜３０％、好ましくは３〜１５％程度である。   The heat shrinkage rate of the heat-shrinkable milky film 4 can be appropriately set according to the shape of the container or the like that is the adherend, but is usually 15% or more in at least one direction. For example, the thermal shrinkage in the case of a uniaxially stretched film is usually about 20 to 90%, preferably about 30 to 70% in the main stretching direction when immersed in hot water at 90 ° C. for 10 seconds. In the case of a biaxially stretched film, the heat shrinkage rate is usually 20 to 90%, preferably about 30 to 70% in one direction (for example, the width direction) when immersed in hot water at 90 ° C. for 10 seconds. In the other direction (for example, the length direction), it is usually 1 to 30%, preferably about 3 to 15%.

本発明の熱収縮性乳白フィルム４は、無彩色の中心層２を有する場合には、紫外領域及び可視領域における光線透過率を極めて小さくできる。例えば、波長２００〜４００ｎｍの領域における光線透過率は、通常３％以下、好ましくは１％以下である。また、波長４００〜６００ｎｍの領域における光線透過率は、通常５％以下であり、３％以下とすることも可能である。この光線透過率は中心層２に含まれる黒色着色剤、白色着色剤等の量や中心層２の厚みなどにより調整できる。   When the heat-shrinkable milky film 4 of the present invention has the achromatic center layer 2, the light transmittance in the ultraviolet region and the visible region can be extremely reduced. For example, the light transmittance in the wavelength region of 200 to 400 nm is usually 3% or less, preferably 1% or less. Further, the light transmittance in the wavelength region of 400 to 600 nm is usually 5% or less, and can be 3% or less. This light transmittance can be adjusted by the amount of black colorant, white colorant, etc. contained in the center layer 2 and the thickness of the center layer 2.

また、本発明の熱収縮性乳白フィルム４は、３８０〜５００ｎｍの波長帯域の光の透過を抑制する有彩色の中心層２を有する場合には、紫外領域及び青緑色の可視領域における光線透過率を極めて小さくできる。波長３８０〜５００ｎｍの領域における光線透過率は、例えば５％以下、好ましくは３％以下である。この光線透過率は中心層２に含まれる黄、赤又は茶系の着色剤の量や中心層２の厚みなどにより調整できる。   Further, when the heat-shrinkable milky film 4 of the present invention has a chromatic color central layer 2 that suppresses transmission of light in the wavelength band of 380 to 500 nm, the light transmittance in the ultraviolet region and the blue-green visible region. Can be made extremely small. The light transmittance in the wavelength region of 380 to 500 nm is, for example, 5% or less, preferably 3% or less. This light transmittance can be adjusted by the amount of yellow, red or brown colorant contained in the center layer 2 and the thickness of the center layer 2.

前記表示印刷インキ層５は商品名等の文字情報やデザイン等を印刷により施した層であり、熱収縮性乳白フィルム４の表層１の表面にインキを用いてグラビア印刷やフレキソ印刷、スクリーン印刷等の慣用の印刷方法により形成できる。インキとしては、特に制限されず、溶剤系インキ、水性インキ等の適宜のインキを選択し、単独で又は２種以上組み合わせて使用することができる。表示印刷インキ層の厚みは、例えば０．５〜２０μｍ、好ましくは１〜１０μｍ程度の範囲から選択することができる。表示印刷インキ層は単層であっても多層であってもよい。表示印刷インキ層の保護等のため、該表示印刷インキ層の表面にさらにオーバーコート層を設けてもよい。また、裏層３の表面（内面側）にも、文字等の表示印刷を施したり、透明インキにより滑り性コート層を設けてもよい。   The display printing ink layer 5 is a layer on which character information such as a product name, design, etc. is applied by printing. Gravure printing, flexographic printing, screen printing, etc. using ink on the surface of the surface layer 1 of the heat-shrinkable milky film 4 The conventional printing method can be used. The ink is not particularly limited, and an appropriate ink such as a solvent-based ink or a water-based ink can be selected and used alone or in combination of two or more. The thickness of the display printing ink layer can be selected from the range of, for example, about 0.5 to 20 μm, preferably about 1 to 10 μm. The display printing ink layer may be a single layer or a multilayer. In order to protect the display printing ink layer, an overcoat layer may be further provided on the surface of the display printing ink layer. Moreover, the surface (inner surface side) of the back layer 3 may be subjected to display printing of characters or the like, or a slip coat layer may be provided with a transparent ink.

本発明のシュリンクラベルは、例えば、熱収縮性乳白フィルム４の表層１の表面に表示印刷インキ層５を形成した後、所望の幅の長尺帯状にスリットし、表示印刷インキ層５側の面を外側にして、主延伸方向が周方向となるように筒状に丸め、両端辺を接着剤や溶剤、ヒートシール等で接着した後、必要に応じて所望の長さに切断し、筒状のシュリンクラベルとすることができる。   The shrink label of the present invention is formed, for example, by forming the display printing ink layer 5 on the surface of the surface layer 1 of the heat-shrinkable milky film 4 and then slitting it into a long strip having a desired width, and the surface on the display printing ink layer 5 side. The outer side is rounded into a cylindrical shape so that the main stretching direction is the circumferential direction, and both ends are bonded with an adhesive, a solvent, heat seal, etc., and then cut into a desired length as necessary. The shrink label can be used.

本発明のラベル付き容器は容器本体に上記本発明のシュリンクラベルが装着されている。容器本体としては、光透過性の材質で形成されていれば特に限定されず、プラスチック製ボトル、ガラス瓶等の何れであってもよい。プラスチック製ボトルとしては、例えば、ポリエステル系樹脂（ポリエチレンテレフタレート、ポリエチレンナフタレートなど）、ポリスチレン系樹脂（ポリスチレンなど）、ポリオレフィン系樹脂（ポリエチレン、ポリプロピレンなど）、ポリ塩化ビニル、ポリカーボネート、アリレート樹脂などのブロー成形可能な熱可塑性樹脂等を素材とすることができる。これらの素材は単独で又は２種以上組み合わせて使用できる。   In the labeled container of the present invention, the shrink label of the present invention is attached to the container body. The container body is not particularly limited as long as it is formed of a light-transmitting material, and may be any of a plastic bottle, a glass bottle, and the like. Examples of plastic bottles include blowers such as polyester resins (polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene resins (polystyrene, etc.), polyolefin resins (polyethylene, polypropylene, etc.), polyvinyl chloride, polycarbonate, and arylate resins. A moldable thermoplastic resin or the like can be used as a material. These materials can be used alone or in combination of two or more.

本発明のラベル付き容器は、例えば、上記筒状に形成されたシュリンクラベルを自動ラベル装着装置に供給し、必要に応じて所望の長さに切断した後、被装着物（容器本体）に連続的に被嵌し、所定温度のスチームトンネルや熱風トンネルを通過させて熱収縮させることにより製造できる。なお、飲料等の内容物の容器への充填時期はシュリンク包装の前後の何れであってもよい。   The container with a label of the present invention, for example, supplies the shrink label formed in the above cylindrical shape to an automatic label mounting apparatus, cuts it to a desired length as necessary, and then continues to an object to be mounted (container body). And can be manufactured by passing through a steam tunnel or hot air tunnel of a predetermined temperature and causing heat shrinkage. In addition, the filling time of the contents such as beverages in the container may be any before and after the shrink wrapping.

本発明のラベル付き容器は、例えば、ビール、清酒、ワイン等のアルコール飲料、牛乳、乳性飲料、緑茶、ビタミン入り飲料などの光によって変色や変質が起こりやすい飲料などの容器として適しているが、裏面が白色であるため、牛乳や乳性飲料等の白色や淡黄色等の淡色系の内容物用容器として特に好ましく用いられる。   The labeled container of the present invention is suitable as a container such as a beverage that easily undergoes discoloration or alteration due to light, such as alcoholic beverages such as beer, sake, wine, milk, milky beverages, green tea, and vitamin-containing beverages. Since the back surface is white, it is particularly preferably used as a container for light-colored contents such as white or light yellow, such as milk and milky beverages.

本発明によれば、熱収縮性乳白フィルムが、３８０〜５００ｎｍの波長帯域（紫外線域〜青緑色の可視光域）の光の透過を抑制する黒色若しくはグレー系又は有彩色の中心層を有するので、飲料等の容器内容物の変色や変質を防止できるとともに、表層が白色であるため、デザイン等の表示印刷を鮮明にでき、しかも裏層が白色であるため、該熱収縮性乳白フィルムを用いたシュリンクラベルを容器に装着した場合、容器内容物が明るくきれいに見え、内容物の外観に優れる。   According to the present invention, the heat-shrinkable milky white film has a black, gray, or chromatic color central layer that suppresses transmission of light in the wavelength band of 380 to 500 nm (ultraviolet region to blue-green visible light region). In addition to preventing discoloration and alteration of the contents of containers such as beverages, since the surface layer is white, display printing such as design can be made clear, and the back layer is white, so the heat-shrinkable milky film is used. When the shrink label is attached to the container, the contents of the container look bright and clean, and the appearance of the contents is excellent.

実施例
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。なお、以下の実施例中、実施例１、実施例２、実施例１０、および実施例１７については参考例として記載した。 EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, in the following examples, Example 1, Example 2, Example 10, and Example 17 were described as reference examples.

実施例１
スチレン−共役ジエンブロックコポリマー［商品名「クリアレン５３０Ｌ」、電気化学工業（株）製］に、酸化チタン（ＴｉＯ2）を６０重量％含有したポリスチレン（ＧＰＰＳ）［商品名「ＳＰＳＭ−７Ｇ９７１」、住化カラー（株）製］マスターバッチを添加、混合して、表層及び裏層形成用のポリスチレン系樹脂組成物［酸化チタン／ポリスチレン系樹脂（重量比）＝５／９５］を調製した。また、スチレン−共役ジエンブロックコポリマー［商品名「クリアレン５３０Ｌ」、電気化学工業（株）製］に、カーボンブラックを４０重量％含有したポリスチレン（ＧＰＰＳ）［商品名「ＳＰＡＢ−８５１」、住化カラー（株）製］マスターバッチを添加、混合して、中心層形成用のポリスチレン系樹脂組成物［カーボンブラック／ポリスチレン系樹脂（重量比）＝１／９９］を調製した。これらの樹脂組成物をＴダイを備えた押出機に供し、温度２２０℃で共押出しし、冷却ロールで冷却した後、長さ方向に１．２倍、幅方向に４倍延伸し、厚み５０μｍ（層の厚みの比：表層／中心層／裏層＝４／３／４）の３層構成の帯状の熱収縮性フィルムを作製した。 Example 1
Styrene-conjugated diene block copolymer [trade name “Clearen 530L”, manufactured by Denki Kagaku Kogyo Co., Ltd.] and polystyrene (GPPS) containing 60 wt% titanium oxide (TiO 2 ) [trade name “SPSM-7G971”, Kabushiki Color Co., Ltd.] master batch was added and mixed to prepare a polystyrene resin composition [titanium oxide / polystyrene resin (weight ratio) = 5/95] for forming the surface layer and the back layer. In addition, polystyrene (GPPS) containing 40% by weight of carbon black in a styrene-conjugated diene block copolymer [trade name “Clearen 530L”, manufactured by Denki Kagaku Kogyo Co., Ltd.] [trade name “SPAB-851”, Sumika Color Co., Ltd. Co., Ltd.] A master batch was added and mixed to prepare a polystyrene resin composition [carbon black / polystyrene resin (weight ratio) = 1/99] for central layer formation. These resin compositions were subjected to an extruder equipped with a T-die, coextruded at a temperature of 220 ° C., cooled with a cooling roll, stretched 1.2 times in the length direction and 4 times in the width direction, and a thickness of 50 μm. A belt-shaped heat-shrinkable film having a three-layer structure of (layer thickness ratio: surface layer / center layer / back layer = 4/3/4) was produced.

この帯状の熱収縮性フィルムの一方の表層の表面にグラビア印刷機によりデザイン印刷と透明オーバーコートを施してシュリンクラベルを得た。このシュリンクラベルを、所定の幅に長さ方向にスリットして複数個のロール状物とした後、各ロール状物を巻き戻して、デザイン面側を外側にしフィルムの幅方向が周方向となるように丸め、両端部を接着剤で接着して長尺筒状とし、これを適宜の長さに切断して筒状シュリンクラベルとした。牛乳を充填した内容積２８０ｍｌのＰＥＴボトルの胴部に前記筒状シュリンクラベルを被せ、スチームトンネルを通して収縮させてラベル付き容器を製造した。   The surface of one surface layer of the belt-like heat-shrinkable film was subjected to design printing and a transparent overcoat by a gravure printing machine to obtain a shrink label. The shrink label is slit to a predetermined width in the length direction to form a plurality of rolls, and then each roll is rewound so that the width direction of the film is the circumferential direction with the design surface side outward. The two ends were bonded with an adhesive to form a long cylindrical shape, which was cut into an appropriate length to obtain a cylindrical shrink label. The cylindrical shrink label was put on the barrel of a PET bottle with an internal volume of 280 ml filled with milk, and the container was contracted through a steam tunnel to produce a labeled container.

実施例２
熱収縮性フィルムの層の厚みの比を表層／中心層／裏層＝３／１／３の３層構成とした点以外は実施例１と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 2
The heat shrinkability of the three-layer structure is the same as that of Example 1 except that the ratio of the thickness of the heat-shrinkable film is a three-layer structure of surface layer / center layer / back layer = 3/1/3. A film was prepared, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat shrinkable film.

実施例３
表層及び裏層形成用のポリスチレン系樹脂組成物の組成比を酸化チタン／ポリスチレン系樹脂（重量比）＝１０／９０としたこと以外は実施例２と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 3
The heat of a three-layer structure was carried out in the same manner as in Example 2 except that the composition ratio of the polystyrene-based resin composition for forming the surface layer and the back layer was changed to titanium oxide / polystyrene-based resin (weight ratio) = 10/90. A shrinkable film was prepared, and a shrink label and a labeled container were produced using the heat-shrinkable film in the same manner as in Example 1.

実施例４
表層及び裏層形成用のポリスチレン系樹脂組成物の組成比を酸化チタン／ポリスチレン系樹脂（重量比）＝２０／８０としたこと以外は実施例２と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 4
The heat of a three-layer structure was carried out in the same manner as in Example 2 except that the composition ratio of the polystyrene resin composition for forming the surface layer and the back layer was titanium oxide / polystyrene resin (weight ratio) = 20/80. A shrinkable film was prepared, and a shrink label and a labeled container were produced using the heat-shrinkable film in the same manner as in Example 1.

実施例５
中心層形成用のポリスチレン系樹脂組成物の組成比をカーボンブラック／ポリスチレン系樹脂（重量比）＝０．１／９９．９としたこと以外は実施例４と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 5
A three-layer construction was carried out in the same manner as in Example 4 except that the composition ratio of the polystyrene resin composition for forming the center layer was carbon black / polystyrene resin (weight ratio) = 0.1 / 99.9. A heat-shrinkable film was produced, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例６
中心層形成用のポリスチレン系樹脂組成物の組成比をカーボンブラック／ポリスチレン系樹脂（重量比）＝０．２／９９．８としたこと以外は実施例４と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 6
A three-layer construction was carried out in the same manner as in Example 4 except that the composition ratio of the polystyrene resin composition for forming the center layer was carbon black / polystyrene resin (weight ratio) = 0.2 / 99.8. A heat-shrinkable film was produced, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

比較例１
中心層形成用のポリスチレン系樹脂組成物の組成比をカーボンブラック／ポリスチレン系樹脂（重量比）＝０／１００としたこと以外は実施例２と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Comparative Example 1
The heat shrinkability of the three-layer structure is the same as in Example 2 except that the composition ratio of the polystyrene resin composition for forming the center layer is carbon black / polystyrene resin (weight ratio) = 0/100. A film was prepared, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat shrinkable film.

比較例２
中心層形成用のポリスチレン系樹脂組成物の組成比をカーボンブラック／ポリスチレン系樹脂（重量比）＝５／９５としたこと以外は実施例２と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Comparative Example 2
The heat shrinkability of a three-layer structure is the same as in Example 2 except that the composition ratio of the polystyrene resin composition for forming the center layer is carbon black / polystyrene resin (weight ratio) = 5/95. A film was prepared, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat shrinkable film.

実施例７
スチレン−共役ジエンブロックコポリマー［商品名「クリアレン５３０Ｌ」、電気化学工業（株）製］に、酸化チタン（ＴｉＯ2）を６０重量％含有したポリスチレン（ＧＰＰＳ）［商品名「ＳＰＳＭ−７Ｇ９７１」、住化カラー（株）製］白色マスターバッチを添加、混合して、表層及び裏層形成用のポリスチレン系樹脂組成物［酸化チタン／ポリスチレン系樹脂（重量比）＝２０／８０］を調製した。また、スチレン−共役ジエンブロックコポリマー［商品名「クリアレン５３０Ｌ」、電気化学工業（株）製］に、前記白色マスターバッチ、及びカーボンブラックを４０重量％含有したポリスチレン（ＧＰＰＳ）［商品名「ＳＰＡＢ−８５１」、住化カラー（株）製］マスターバッチを添加、混合して、中心層形成用のポリスチレン系樹脂組成物［酸化チタン／カーボンブラック／ポリスチレン系樹脂（重量比）＝２０／０．０５／７９．９５］を調製した。これらの樹脂組成物をＴダイを備えた押出機に供し、温度２１０℃で共押出しし、冷却ロールで冷却した後、長さ方向に１．２倍、幅方向に４倍延伸し、厚み５０μｍ（層の厚みの比：表層／中心層／裏層＝３／１／３）の３層構成の帯状の熱収縮性フィルムを作製した。 Example 7
Styrene-conjugated diene block copolymer [trade name “Clearen 530L”, manufactured by Denki Kagaku Kogyo Co., Ltd.] and polystyrene (GPPS) containing 60 wt% titanium oxide (TiO 2 ) [trade name “SPSM-7G971”, Kana Color Co., Ltd.] White masterbatch was added and mixed to prepare a polystyrene-based resin composition [titanium oxide / polystyrene-based resin (weight ratio) = 20/80] for forming the front and back layers. Also, polystyrene (GPPS) containing 40 wt% of the white masterbatch and carbon black in a styrene-conjugated diene block copolymer [trade name “Clearen 530L”, manufactured by Denki Kagaku Kogyo Co., Ltd.] [trade name “SPAB- 851 ", manufactured by Sumika Color Co., Ltd.] A master batch was added and mixed to form a polystyrene resin composition for forming a central layer [titanium oxide / carbon black / polystyrene resin (weight ratio) = 20 / 0.05. /79.95] was prepared. These resin compositions were subjected to an extruder equipped with a T die, coextruded at a temperature of 210 ° C., cooled with a cooling roll, stretched 1.2 times in the length direction and 4 times in the width direction, and a thickness of 50 μm. A belt-shaped heat-shrinkable film having a three-layer structure (layer thickness ratio: surface layer / center layer / back layer = 3/1/3) was produced.

この熱収縮性フィルムを用いて、実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。   Using this heat-shrinkable film, a shrink label and a labeled container were produced in the same manner as in Example 1.

実施例８
中心層形成用のポリスチレン系樹脂組成物の組成比を酸化チタン／カーボンブラック／ポリスチレン系樹脂（重量比）＝２０／０．２／７９．８としたこと以外は実施例７と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 8
The same operation as in Example 7 was performed except that the composition ratio of the polystyrene resin composition for forming the center layer was changed to titanium oxide / carbon black / polystyrene resin (weight ratio) = 20 / 0.2 / 79.8. A heat-shrinkable film having a three-layer structure was prepared, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例９
中心層形成用のポリスチレン系樹脂組成物の組成比を酸化チタン／カーボンブラック／ポリスチレン系樹脂（重量比）＝２０／１／７９としたこと以外は実施例７と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 9
Three layers were formed by performing the same operation as in Example 7 except that the composition ratio of the polystyrene resin composition for forming the center layer was titanium oxide / carbon black / polystyrene resin (weight ratio) = 20/1/79. A heat-shrinkable film having the structure was produced, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例１０
中心層形成用のポリスチレン系樹脂組成物の組成比を酸化チタン／カーボンブラック／ポリスチレン系樹脂（重量比）＝２０／５／７５としたこと以外は実施例７と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 10
Three layers were formed by performing the same operation as in Example 7 except that the composition ratio of the polystyrene resin composition for forming the center layer was titanium oxide / carbon black / polystyrene resin (weight ratio) = 20/5/75. A heat-shrinkable film having the structure was produced, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例１１
スチレン−共役ジエンブロックコポリマー［商品名「クリアレン５３０Ｌ」、電気化学工業（株）製］に、酸化チタン（ＴｉＯ2）を６０重量％含有したポリスチレン（ＧＰＰＳ）［商品名「ＳＰＳＭ−７Ｇ９７１」、住化カラー（株）製］白色マスターバッチを添加、混合して、表層及び裏層形成用のポリスチレン系樹脂組成物［酸化チタン／ポリスチレン系樹脂（重量比）＝２４／７６］を調製した。また、スチレン−共役ジエンブロックコポリマー［商品名「クリアレン５３０Ｌ」、電気化学工業（株）製］に、前記白色マスターバッチ、及びカーボンブラックを４０重量％含有したポリスチレン（ＧＰＰＳ）［商品名「ＳＰＡＢ−８５１」、住化カラー（株）製］マスターバッチを添加、混合して、中心層形成用のポリスチレン系樹脂組成物［酸化チタン／カーボンブラック／ポリスチレン系樹脂（重量比）＝２０／０．２／７９．８］を調製した。これらの樹脂組成物をＴダイを備えた押出機に供し、温度２１０℃で共押出しし、冷却ロールで冷却した後、長さ方向に１．２倍、幅方向に４倍延伸し、厚み５０μｍ（層の厚みの比：表層／中心層／裏層＝３／１／３）の３層構成の帯状の熱収縮性フィルムを作製した。 Example 11
Styrene-conjugated diene block copolymer [trade name “Clearen 530L”, manufactured by Denki Kagaku Kogyo Co., Ltd.] and polystyrene (GPPS) containing 60 wt% titanium oxide (TiO 2 ) [trade name “SPSM-7G971”, Kana Color Co., Ltd.] White masterbatch was added and mixed to prepare a polystyrene-based resin composition [titanium oxide / polystyrene-based resin (weight ratio) = 24/76] for forming the front and back layers. Also, polystyrene (GPPS) containing 40 wt% of the white masterbatch and carbon black in a styrene-conjugated diene block copolymer [trade name “Clearen 530L”, manufactured by Denki Kagaku Kogyo Co., Ltd.] [trade name “SPAB- 851 ", manufactured by Sumika Color Co., Ltd.] A master batch was added and mixed to form a polystyrene resin composition for forming the central layer [titanium oxide / carbon black / polystyrene resin (weight ratio) = 20 / 0.2. /79.8] was prepared. These resin compositions were subjected to an extruder equipped with a T die, coextruded at a temperature of 210 ° C., cooled with a cooling roll, stretched 1.2 times in the length direction and 4 times in the width direction, and a thickness of 50 μm. A belt-shaped heat-shrinkable film having a three-layer structure (layer thickness ratio: surface layer / center layer / back layer = 3/1/3) was produced.

この熱収縮性フィルムを用いて、実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。   Using this heat-shrinkable film, a shrink label and a labeled container were produced in the same manner as in Example 1.

実施例１２
中心層形成用のポリスチレン系樹脂組成物の組成比を酸化チタン／カーボンブラック／ポリスチレン系樹脂（重量比）＝２０／０．１５／７９．８５としたこと以外は実施例１１と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 12
The same operation as in Example 11 was performed except that the composition ratio of the polystyrene resin composition for forming the center layer was changed to titanium oxide / carbon black / polystyrene resin (weight ratio) = 20 / 0.15 / 79.85. A heat-shrinkable film having a three-layer structure was prepared, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例１３
中心層形成用のポリスチレン系樹脂組成物の組成比を酸化チタン／カーボンブラック／ポリスチレン系樹脂（重量比）＝２０／０．１／７９．９としたこと以外は実施例１１と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 13
The same operation as in Example 11 was performed except that the composition ratio of the polystyrene resin composition for forming the center layer was changed to titanium oxide / carbon black / polystyrene resin (weight ratio) = 20 / 0.1 / 79.9. A heat-shrinkable film having a three-layer structure was prepared, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

比較例３
中心層形成用のポリスチレン系樹脂組成物の組成比を酸化チタン／カーボンブラック／ポリスチレン系樹脂（重量比）＝０／０／１００としたこと以外は実施例１１と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Comparative Example 3
Three layers were formed in the same manner as in Example 11 except that the composition ratio of the polystyrene resin composition for forming the center layer was titanium oxide / carbon black / polystyrene resin (weight ratio) = 0/0/100. A heat-shrinkable film having the structure was produced, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

比較例４
中心層形成用のポリスチレン系樹脂組成物の組成比を酸化チタン／カーボンブラック／ポリスチレン系樹脂（重量比）＝２０／１０／７０としたこと以外は実施例１１と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Comparative Example 4
Three layers were formed by performing the same operation as in Example 11 except that the composition ratio of the polystyrene resin composition for forming the center layer was titanium oxide / carbon black / polystyrene resin (weight ratio) = 20/10/70. A heat-shrinkable film having the structure was produced, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例１４
ポリエチレンテレフタレート系樹脂（ＰＥＴ樹脂）［商品名「Ｅｍｂｒａｃｅ」、イーストマンケミカル社製］に、酸化チタン（ＴｉＯ2）を５０重量％含有したＰＥＴ樹脂［商品名「ＥＰＭ−７６７０」、住化カラー（株）製］白色マスターバッチを添加、混合して、表層及び裏層形成用のポリエチレンテレフタレート樹脂組成物［酸化チタン／ＰＥＴ樹脂（重量比）＝２０／８０］を調製した。また、ＰＥＴ樹脂［商品名「Ｅｍｂｒａｃｅ」、イーストマンケミカル社製］に、前記白色マスターバッチ、及びカーボンブラックを３０重量％含有したＰＥＴ樹脂［商品名「ＥＰＭ−８４００」、住化カラー（株）製］マスターバッチを添加、混合して、中心層形成用のポリエチレンテレフタレート樹脂組成物［酸化チタン／カーボンブラック／ＰＥＴ樹脂（重量比）＝２０／０．０５／７９．９５］を調製した。これらの樹脂組成物をＴダイを備えた押出機に供し、温度２５０℃で共押出しし、冷却ロールで冷却した後、幅方向に４．５倍延伸し、厚み５０μｍ（層の厚みの比：表層／中心層／裏層＝３／１／３）の３層構成の帯状の熱収縮性フィルムを作製した。 Example 14
Polyethylene terephthalate resin (PET resin) [trade name “Embrace”, manufactured by Eastman Chemical Co., Ltd.] and PET resin containing 50 wt% titanium oxide (TiO 2 ) [trade name “EPM-7670”, Sumika Color ( Co., Ltd.] White masterbatch was added and mixed to prepare a polyethylene terephthalate resin composition [titanium oxide / PET resin (weight ratio) = 20/80] for forming the surface layer and the back layer. Further, PET resin [trade name “EPM-8400”, Sumika Color Co., Ltd.] containing PET resin [trade name “Embrace”, manufactured by Eastman Chemical Co., Ltd.] and 30% by weight of the white masterbatch and carbon black. Product] A master batch was added and mixed to prepare a polyethylene terephthalate resin composition [titanium oxide / carbon black / PET resin (weight ratio) = 20 / 0.05 / 79.95] for forming the center layer. These resin compositions were subjected to an extruder equipped with a T die, coextruded at a temperature of 250 ° C., cooled with a cooling roll, then stretched 4.5 times in the width direction, and a thickness of 50 μm (ratio of layer thickness: A belt-shaped heat-shrinkable film having a three-layer structure of surface layer / center layer / back layer = 3/1/3) was produced.

この熱収縮性フィルムを用いて、実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。   Using this heat-shrinkable film, a shrink label and a labeled container were produced in the same manner as in Example 1.

実施例１５
中心層形成用のポリエチレンテレフタレート樹脂組成物の組成比を酸化チタン／カーボンブラック／ＰＥＴ樹脂（重量比）＝２０／０．２／７９．８としたこと以外は実施例１４と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 15
The same operation as in Example 14 was performed except that the composition ratio of the polyethylene terephthalate resin composition for forming the center layer was changed to titanium oxide / carbon black / PET resin (weight ratio) = 20 / 0.2 / 79.8. A heat-shrinkable film having a three-layer structure was prepared, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例１６
中心層形成用のポリエチレンテレフタレート樹脂組成物の組成比を酸化チタン／カーボンブラック／ＰＥＴ樹脂（重量比）＝２０／１／７９としたこと以外は実施例１４と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 16
A three-layer construction was carried out in the same manner as in Example 14 except that the composition ratio of the polyethylene terephthalate resin composition for forming the center layer was titanium oxide / carbon black / PET resin (weight ratio) = 20/1/79. A heat-shrinkable film was produced, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例１７
中心層形成用のポリエチレンテレフタレート樹脂組成物の組成比を酸化チタン／カーボンブラック／ＰＥＴ樹脂（重量比）＝２０／５／７５としたこと以外は実施例１４と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 17
A three-layer construction was carried out in the same manner as in Example 14 except that the composition ratio of the polyethylene terephthalate resin composition for forming the center layer was titanium oxide / carbon black / PET resin (weight ratio) = 20/5/75. A heat-shrinkable film was produced, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

比較例５
中心層形成用のポリエチレンテレフタレート樹脂組成物の組成比を酸化チタン／カーボンブラック／ＰＥＴ樹脂（重量比）＝０／０／１００としたこと以外は実施例１４と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Comparative Example 5
A three-layer construction was carried out in the same manner as in Example 14 except that the composition ratio of the polyethylene terephthalate resin composition for forming the center layer was titanium oxide / carbon black / PET resin (weight ratio) = 0/0/100. A heat-shrinkable film was produced, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

比較例６
中心層形成用のポリエチレンテレフタレート樹脂組成物の組成比を酸化チタン／カーボンブラック／ＰＥＴ樹脂（重量比）＝０／５／９５とし、裏層を設けなかったこと以外は実施例１４と同様の操作を行って２層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Comparative Example 6
The same operation as in Example 14 except that the composition ratio of the polyethylene terephthalate resin composition for forming the center layer was titanium oxide / carbon black / PET resin (weight ratio) = 0/5/95 and no back layer was provided. A heat-shrinkable film having a two-layer structure was produced, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例１８
スチレン−共役ジエンブロックコポリマー［商品名「クリアレン５３０Ｌ」、電気化学工業（株）製］に、酸化チタン（ＴｉＯ2）を６０重量％含有したポリスチレン（ＧＰＰＳ）［商品名「ＳＰＳＭ−７Ｇ９７１」、住化カラー（株）製］マスターバッチを添加、混合して、表層及び裏層形成用のポリスチレン系樹脂組成物［酸化チタン／ポリスチレン系樹脂（重量比）＝１０／９０］を調製した。また、スチレン−共役ジエンブロックコポリマー［商品名「クリアレン５３０Ｌ」、電気化学工業（株）製］に、該ポリマーに対し展着剤として０．５重量％の流動パラフィンを添加し、その後、赤顔料［商品名「ＳＨＰＡ−１０２」、住化カラー（株）製、有機系（アゾ系顔料）］を添加、混合して、中心層形成用のポリスチレン系樹脂組成物［赤顔料／ポリスチレン系樹脂（重量比）＝０．５／９９．５］を調製した。これらの樹脂組成物をＴダイを備えた押出機に供し、温度２２０℃で共押出しし、冷却ロールで冷却した後、長さ方向に１．２倍、幅方向に４倍延伸し、厚み５０μｍ（層の厚みの比：表層／中心層／裏層＝２／１／２）の３層構成の帯状の熱収縮性フィルムを作製した。 Example 18
Styrene-conjugated diene block copolymer [trade name “Clearen 530L”, manufactured by Denki Kagaku Kogyo Co., Ltd.] and polystyrene (GPPS) containing 60 wt% titanium oxide (TiO 2 ) [trade name “SPSM-7G971”, Kabushiki Color Co., Ltd.] master batch was added and mixed to prepare a polystyrene resin composition [titanium oxide / polystyrene resin (weight ratio) = 10/90] for forming the surface layer and the back layer. Further, 0.5% by weight of liquid paraffin as a spreading agent is added to the styrene-conjugated diene block copolymer [trade name “Clearen 530L”, manufactured by Denki Kagaku Kogyo Co., Ltd.], and then a red pigment. [Product name “SHPA-102”, manufactured by Sumika Color Co., Ltd., organic (azo pigment)] was added and mixed to form a polystyrene resin composition [red pigment / polystyrene resin (for forming a central layer). Weight ratio) = 0.5 / 99.5]. These resin compositions were subjected to an extruder equipped with a T-die, coextruded at a temperature of 220 ° C., cooled with a cooling roll, stretched 1.2 times in the length direction and 4 times in the width direction, and a thickness of 50 μm. A belt-like heat-shrinkable film having a three-layer structure of (layer thickness ratio: surface layer / center layer / back layer = 2/1/2) was produced.

この熱収縮性フィルムを用いて、実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。   Using this heat-shrinkable film, a shrink label and a labeled container were produced in the same manner as in Example 1.

実施例１９
赤顔料［商品名「ＳＨＰＡ−１０２」、住化カラー（株）製、有機系］の代わりに、黄顔料［商品名「ＳＨＰＡ−３４７」、住化カラー（株）製、無機系（クロムイエロー）］を用いて、中心層形成用のポリスチレン系樹脂組成物［黄顔料／ポリスチレン系樹脂（重量比）＝１．０／９９．０］を調製した点以外は実施例１８と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 19
Instead of red pigment [trade name “SHPA-102”, manufactured by Sumika Color Co., Ltd., organic], yellow pigment [trade name “SHPA-347”, manufactured by Sumika Color Co., Ltd., inorganic (chrome yellow) )] Was used to perform the same operations as in Example 18 except that a polystyrene resin composition [yellow pigment / polystyrene resin (weight ratio) = 1.0 / 99.0] for forming the center layer was prepared. A heat-shrinkable film having a three-layer structure was prepared, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例２０
赤顔料［商品名「ＳＨＰＡ−１０２」、住化カラー（株）製、有機系］の代わりに、茶顔料［商品名「ＳＨＰＡ−９１８」、住化カラー（株）製、無機系（ベンガラ）］を用いて、中心層形成用のポリスチレン系樹脂組成物［茶顔料／ポリスチレン系樹脂（重量比）＝１．０／９９．０］を調製した点以外は実施例１８と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 20
Instead of red pigment [trade name “SHPA-102”, manufactured by Sumika Color Co., Ltd., organic], brown pigment [trade name “SHPA-918”, manufactured by Sumika Color Co., Ltd., inorganic (Bengara) The same operations as in Example 18 were performed except that a polystyrene resin composition [tea pigment / polystyrene resin (weight ratio) = 1.0 / 99.0] for forming the center layer was prepared. A heat-shrinkable film having a three-layer structure was prepared, and a shrink label and a labeled container were produced in the same manner as in Example 1 using this heat-shrinkable film.

実施例２１
赤顔料［商品名「ＳＨＰＡ−１０２」、住化カラー（株）製、有機系］とともに白顔料［酸化チタン（ＴｉＯ2）］を用いて、中心層形成用のポリスチレン系樹脂組成物［赤顔料／白顔料／ポリスチレン系樹脂（重量比）＝０．５／５．０／９４．５］を調製した点以外は実施例１８と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 21
A white pigment [titanium oxide (TiO 2 )] is used together with a red pigment [trade name “SHPA-102”, manufactured by Sumika Color Co., Ltd., organic type], and a polystyrene resin composition [red pigment for forming a central layer] / White pigment / polystyrene resin (weight ratio) = 0.5 / 5.0 / 94.5] The same operation as in Example 18 was performed to prepare a heat-shrinkable film having a three-layer structure. Further, using this heat-shrinkable film, a shrink label and a labeled container were produced in the same manner as in Example 1.

実施例２２
赤顔料［商品名「ＳＨＰＡ−１０２」、住化カラー（株）製、有機系］の代わりに、茶顔料［商品名「ＳＨＰＡ−９１８」、住化カラー（株）製、無機系（ベンガラ）］と白顔料［酸化チタン（ＴｉＯ2）］とを用いて、中心層形成用のポリスチレン系樹脂組成物［茶顔料／白顔料／ポリスチレン系樹脂（重量比）＝１．０／５．０／９４．０］を調製した点以外は実施例１８と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Example 22
Instead of red pigment [trade name “SHPA-102”, manufactured by Sumika Color Co., Ltd., organic], brown pigment [trade name “SHPA-918”, manufactured by Sumika Color Co., Ltd., inorganic (Bengara) ] And a white pigment [titanium oxide (TiO 2 )], a polystyrene resin composition [tea pigment / white pigment / polystyrene resin (weight ratio) = 1.0 / 5.0 / 94.0] was performed in the same manner as in Example 18 to produce a heat-shrinkable film having a three-layer structure, and further using this heat-shrinkable film in the same manner as in Example 1, a shrink label And a labeled container was produced.

比較例７
赤顔料［商品名「ＳＨＰＡ−１０２」、住化カラー（株）製、有機系］を用いずに、中心層形成用のポリスチレン系樹脂組成物［赤顔料／ポリスチレン系樹脂（重量比）＝０／１００］を調製した点以外は実施例１８と同様の操作を行って３層構成の熱収縮性フィルムを作製し、さらにこの熱収縮性フィルムを用いて実施例１と同様にしてシュリンクラベル及びラベル付き容器を製造した。 Comparative Example 7
Without using a red pigment [trade name “SHPA-102”, manufactured by Sumika Color Co., Ltd., organic], a polystyrene resin composition for forming a central layer [red pigment / polystyrene resin (weight ratio) = 0. / 100] was carried out in the same manner as in Example 18 to produce a heat-shrinkable film having a three-layer structure, and further using this heat-shrinkable film in the same manner as in Example 1, A labeled container was produced.

評価試験
実施例及び比較例で得られた熱収縮性フィルムについて下記の評価試験を行った。その結果を表１に示す。表中、「ＰＳ」はポリスチレン系樹脂を、「ＣＢ」はカーボンブラックを、「ＴｉＯ2」は酸化チタンを、「ＰＥＴ」はポリエチレンテレフタレート系樹脂を意味する。フィルム構成の欄の「表」、「中心」及び「裏」は、それぞれ、表層、中心層及び裏層を構成する樹脂組成物を意味する。表中の数字は割合を示す。 Evaluation test The following evaluation test was done about the heat-shrinkable film obtained by the Example and the comparative example. The results are shown in Table 1. In the table, “PS” means polystyrene resin, “CB” means carbon black, “TiO 2 ” means titanium oxide, and “PET” means polyethylene terephthalate resin. “Front”, “center”, and “back” in the column of the film configuration mean the resin composition constituting the surface layer, the center layer, and the back layer, respectively. The numbers in the table indicate percentages.

（遮光性）
実施例及び比較例で得られた各熱収縮性フィルムにつき、波長２００〜１０００ｎｍの範囲の光線透過率を、近赤外、紫外、可視分光光度計［商品名「ＵＶ−３１０１ＰＣ」、（株）島津製作所製］により測定し、以下の基準で特定波長帯域の遮光性を評価した。 (Light shielding)
For each heat-shrinkable film obtained in Examples and Comparative Examples, the light transmittance in the wavelength range of 200 to 1000 nm was measured using a near-infrared, ultraviolet, and visible spectrophotometer [trade name “UV-3101PC”, Inc. Manufactured by Shimadzu Corporation], and the light-shielding property in a specific wavelength band was evaluated according to the following criteria.

なお、図２に実施例２、実施例３、実施例４及び比較例１で得られた熱収縮性フィルムの光線透過率の測定結果を示す。図２中、ａ、ｂ、ｃ及びｄは、それぞれ、実施例４、実施例３、実施例２及び比較例１で得られた熱収縮性フィルムについての測定結果を示す。   In addition, the measurement result of the light transmittance of the heat-shrinkable film obtained in Example 2, Example 3, Example 4, and Comparative Example 1 is shown in FIG. In FIG. 2, a, b, c, and d show the measurement results for the heat-shrinkable films obtained in Example 4, Example 3, Example 2, and Comparative Example 1, respectively.

また、図３に実施例１１、実施例１２、実施例１３及び比較例３で得られた熱収縮性フィルムの光線透過率（透過度）の測定結果を示す。図３中、ａ、ｂ、ｃ及びｄは、それぞれ、実施例１１、実施例１２、実施例１３及び比較例３で得られた熱収縮性フィルムについての測定結果を示す。   Moreover, the measurement result of the light transmittance (transmittance) of the heat-shrinkable film obtained in Example 11, Example 12, Example 13, and Comparative Example 3 is shown in FIG. In FIG. 3, a, b, c, and d show the measurement results for the heat-shrinkable films obtained in Example 11, Example 12, Example 13, and Comparative Example 3, respectively.

図４に比較例７、実施例１８、実施例１９、実施例２０、実施例２１及び実施例２２で得られた熱収縮性フィルムの光線透過率（透過度）の測定結果を示す。図４中、ａ、ｂ、ｃ、ｄ、ｅ及びｆは、それぞれ、比較例７、実施例１８、実施例１９、実施例２０、実施例２１及び実施例２２で得られた熱収縮性フィルムについての測定結果を示す。   FIG. 4 shows the measurement results of the light transmittance (transmittance) of the heat-shrinkable films obtained in Comparative Example 7, Example 18, Example 19, Example 20, Example 21, and Example 22. In FIG. 4, a, b, c, d, e and f are the heat-shrinkable films obtained in Comparative Example 7, Example 18, Example 19, Example 20, Example 21 and Example 22, respectively. The measurement result about is shown.

［実施例１〜１７及び比較例１〜６（表１〜３）の評価基準］
◎：波長２００〜６００ｎｍの領域での光線透過率が３％以下である。
○：波長２００〜６００ｎｍの領域での光線透過率が３％を越え、且つ５％以下である。
×：波長２００〜６００ｎｍの領域での光線透過率が５％を超える。 [Evaluation criteria of Examples 1 to 17 and Comparative Examples 1 to 6 (Tables 1 to 3)]
A: The light transmittance in a wavelength range of 200 to 600 nm is 3% or less.
A: The light transmittance in the wavelength range of 200 to 600 nm exceeds 3% and is 5% or less.
X: Light transmittance in a wavelength range of 200 to 600 nm exceeds 5%.

［実施例１８〜２２及び比較例７（表４）の評価基準］
○：波長３８０〜５００ｎｍの領域での光線透過率が５％以下である。
×：波長３８０〜５００ｎｍの領域での光線透過率が５％を超える。 [Evaluation criteria of Examples 18 to 22 and Comparative Example 7 (Table 4)]
A: The light transmittance in the wavelength range of 380 to 500 nm is 5% or less.
X: The light transmittance in a wavelength range of 380 to 500 nm exceeds 5%.

（白度）
実施例及び比較例で得られた各熱収縮性フィルムにつき、表層側の表面を、紫外可視分光光度計［商品名「ＵＶ−２４５０」（株）島津製作所製］を用いてＪＩＳ Ｚ ８７１５に準じて測定し、標準白色板（財団法人日本色彩研究所製）の測定値をＷ値１００として、以下の基準でフィルムの白度を評価した。
◎：Ｗ値８０以上
○：Ｗ値７５以上８０未満
△：Ｗ値６０以上７５未満
×：Ｗ値６０未満 (Whiteness)
About each heat-shrinkable film obtained in Examples and Comparative Examples, the surface of the surface layer side is in accordance with JIS Z 8715 using an ultraviolet-visible spectrophotometer [trade name “UV-2450” (manufactured by Shimadzu Corporation)]. The whiteness of the film was evaluated according to the following criteria, with the measured value of a standard white plate (manufactured by Japan Color Research Institute) as W value 100.
◎: W value of 80 or more ○: W value of 75 or more and less than 80 Δ: W value of 60 or more and less than 75 ×: W value of less than 60

これらを目視評価したところ、Ｗ値７５以上（◎及び○）では、表面が白くデザインが鮮明であって、中心層の黒色やグレー系の色、有彩色がほとんど気にならない程度であり、Ｗ値６０以上７５未満（△）では、表面が若干グレーがかった白色となるか、又は有彩色が僅かに認められるが、デザインは鮮明であり、また、Ｗ値が６０未満（×）では、表面が黒っぽいグレーとなりデザインが暗く見えるか、表面に有彩色がはっきり認められた。   When these were visually evaluated, when the W value was 75 or more (◎ and ○), the surface was white and the design was clear, and the black, gray color, and chromatic color of the center layer were hardly worried. When the value is 60 or more and less than 75 (△), the surface is slightly grayish white or a slight chromatic color is recognized, but the design is clear, and when the W value is less than 60 (×), the surface The blackish gray and the design look dark, or chromatic colors are clearly recognized on the surface.

（内容物の外観性）
実施例及び比較例で得られたラベル付き容器の口から内容物（牛乳）を覗き、内容物の外観を以下の基準で目視評価した。
○：白く新鮮に見える。
×：牛乳の色が黒っぽく見えるか、又は有彩色が認められる。 (Appearance of contents)
The contents (milk) were looked into from the mouths of the labeled containers obtained in Examples and Comparative Examples, and the appearance of the contents was visually evaluated according to the following criteria.
○: It looks white and fresh.
X: The color of milk looks dark or a chromatic color is recognized.

Figure 0004464356
Figure 0004464356

Figure 0004464356
Figure 0004464356

Figure 0004464356
Figure 0004464356

Figure 0004464356
Figure 0004464356

産業上の利用可能性
以上のように、本発明の熱収縮性乳白フィルムは、飲料等の容器内容物の変色や変質を防止できるとともに、表層のデザイン等の表示印刷を鮮明にできる。さらに、本発明の熱収縮性乳白フィルムを用いたシュリンクラベルは、容器に装着した場合に、容器内容物を見たときの印象に優れ、飲料等が本来の色を損なわず違和感なく見えるラベルとして極めて有用である。 INDUSTRIAL APPLICABILITY As described above, the heat-shrinkable milky white film of the present invention can prevent discoloration and alteration of the contents of containers such as beverages and can clearly display and print the surface layer design. Furthermore, the shrink label using the heat-shrinkable milky film of the present invention is a label that, when attached to a container, has an excellent impression when looking at the contents of the container, and beverages and the like can be seen without feeling uncomfortable without losing the original color. Very useful.

Claims (7)

無彩色の中心層と、白色の表裏層とを有する熱収縮性乳白フィルムであって、
中心層が黒色着色剤として使用されるカーボンブラックを含み、該カーボンブラックの
含有量は中心層全体の０．０１〜３重量％であり、
白色の表裏層の各々が独立して白色着色剤として酸化チタンを含み、該酸化チタンの含
有量は、各層の総量の１０〜４０重量％であり、
該フィルムは、表裏層と中心層とを共押出し成形し、次いで延伸処理することにより形
成され、
表裏層および中心層の各々が熱収縮性フィルム層であり、
該中心層の厚みはフィルム全体の厚みに対して５〜３０％であり、
該フィルムは、３８０〜５００ｎｍの波長帯域の光の透過率が５％以下であり、
該フィルムの熱収縮率は、９０℃の熱水に１０秒間浸漬したときに一方の方向において２０〜９０％であり、
該フィルムの表面の白度が、ＪＩＳ Ｚ ８７１５に準じて測定され、標準白色板の測定値であるＷ値１００に対する相対値として表された場合に、Ｗ値７５以上で表される、熱収縮性乳白フィルム。A heat-shrinkable milky film having an achromatic center layer and a white front and back layer,
The center layer contains carbon black used as a black colorant, and the content of the carbon black is 0.01 to 3% by weight of the entire center layer,
Each of the white front and back layers independently contains titanium oxide as a white colorant, and the content of the titanium oxide is 10 to 40% by weight of the total amount of each layer,
The film is formed by co-extrusion of the front and back layers and the center layer, and then stretching.
Each of the front and back layers and the center layer is a heat-shrinkable film layer,
The thickness of the central layer is 5 to 30% with respect to the thickness of the entire film,
The film has a light transmittance of 5% or less in a wavelength band of 380 to 500 nm,
The thermal contraction rate of the film is 20 to 90% in one direction when immersed in hot water at 90 ° C. for 10 seconds,
White of the surface of the film is measured in accordance with JIS Z 871 5, when expressed as a relative value with respect to the W value 100 is a measure of the standard white plate, it is expressed by W value 75 or more, heat Shrinkable milky film. カーボンブラックの含有量が中心層全体の０．１５〜３重量％であり、２００〜６００ｎｍの波長帯域の光の透過率が３％以下である、請求項１に記載の熱収縮性乳白フィルム。2. The heat-shrinkable milky film according to claim 1, wherein the carbon black content is 0.15 to 3% by weight of the entire central layer, and the light transmittance in the wavelength band of 200 to 600 nm is 3% or less. 中心層がさらに白色着色剤を含み、該白色着色剤の含有量が中心層全体の１〜４０重量％である、請求項１または２に記載の熱収縮性乳白フィルム。The heat-shrinkable milky film according to claim 1 or 2, wherein the center layer further contains a white colorant, and the content of the white colorant is 1 to 40% by weight of the entire center layer. ３８０〜５００ｎｍの波長帯域の光の透過を抑制する有彩色の中心層と、白色の表裏層とを有する熱収縮性乳白フィルムであって、
中心層が有彩色着色剤として黄、赤又は茶系の顔料を少なくとも１種類含み、その含有量が、中心層全体の０．０１〜１重量％であり、
白色の表裏層の各々が独立して白色着色剤として酸化チタンを含み、該酸化チタンの含有量は、各層の総量の５〜４０重量％であり、
該フィルムは、表裏層と中心層とを共押出し成形し、次いで延伸処理することにより形成され、
表裏層および中心層の各々が熱収縮性フィルム層であり、
該中心層の厚みはフィルム全体の厚みに対して５〜３０％であり、
該フィルムは、３８０〜５００ｎｍの波長帯域の光の透過率が５％以下であり、
該フィルムの熱収縮率は、９０℃の熱水に１０秒間浸漬したときに一方の方向において２０〜９０％であり、
該フィルムの表面の白度が、ＪＩＳ Ｚ ８７１５に準じて測定され、標準白色板の測定値であるＷ値１００に対する相対値として表された場合に、Ｗ値７５以上で表される、熱収縮性乳白フィルム。A heat-shrinkable milky film having a chromatic color central layer that suppresses transmission of light in a wavelength band of 380 to 500 nm, and a white front and back layer,
The center layer contains at least one yellow, red or brown pigment as a chromatic colorant, and the content thereof is 0.01 to 1 % by weight of the entire center layer,
Each of the white front and back layers independently contains titanium oxide as a white colorant, and the content of the titanium oxide is 5 to 40% by weight of the total amount of each layer,
The film is formed by co-extrusion of the front and back layers and the center layer, and then stretching.
Each of the front and back layers and the center layer is a heat-shrinkable film layer,
The thickness of the central layer is 5 to 30% with respect to the thickness of the entire film,
The film has a light transmittance of 5% or less in a wavelength band of 380 to 500 nm,
The thermal contraction rate of the film is 20 to 90% in one direction when immersed in hot water at 90 ° C. for 10 seconds,
White of the surface of the film is measured in accordance with JIS Z 871 5, when expressed as a relative value with respect to the W value 100 is a measure of the standard white plate, it is expressed by W value 75 or more, heat Shrinkable milky film. 中心層がさらに白色着色剤を含み、白色着色剤の含有量が中心層全体の０．１〜４０重量％である、請求項４に記載の熱収縮性乳白フィルム。The heat-shrinkable milky film according to claim 4 , wherein the center layer further contains a white colorant, and the content of the white colorant is 0.1 to 40% by weight of the entire center layer. 請求項１〜５のいずれかの項に記載の熱収縮性乳白フィルムおよび該フィルムの表層側の表面に表示印刷インキ層を有するシュリンクラベル。A heat-shrinkable milky-white film according to any one of claims 1 to 5 and a shrink label having a display printing ink layer on the surface on the surface layer side of the film. 請求項６に記載のシュリンクラベルを容器本体に装着したラベル付き容器。A labeled container in which the shrink label according to claim 6 is mounted on a container body.
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